Department of Chemistry and Chemical Biology

Indian Institute of Technology (ISM)

Dhanbad - 826004

LABORATORY MANUAL
FOR

3rd Semester M.Sc. Chemistry

(CYC 517: Physical Chemistry Lab –II)

Location: Science Block, 1st Floor, PG laboratory,

Department of Chemistry and Chemical Biology
 TABLE OF CONTENTS

Page no
Introduction to the Lab 2-3
Laboratory Safety Guideline 4
Experiment 1 Calculation of Photoluminescence Quantum 5-7
Yield.
Experiment 2 Synthesis of fluorescent carbon quantum dots 8-9
from lemon juice and study of its optical
property.
Experiment 3 Spectroscopic determination of Critical 10-11
Micelle Concentration.
Experiment 4 Functional group determination of surface 12-14
modified nanoparticles using IR spectroscopy.
Experiment 5 Estimation of band-gap for Cu nanoparticles 15-16
using absorption spectroscopy
Experiment 6 Study on the effect of extended conjugation on 17-18
the wavelength of maximum absorption of
organic compounds.
Experiment 7 Determination of thermodynamic parameters 19-21
for the reaction by EMF method.
Experiment 8 Determination of the surface area of silica by 22-23
N2 adsorption at 77K.
Experiment 9 Precipitation titration and determination of 24-26
solubility of a sparingly soluble salt.
Experiment 10 Determination of the concentration of a given 27-39
solution using Cyclic Voltametry.
Experiment 11 Potential Energy Surface Calculation 30-34

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Introduction
This course will introduce you to various instrumental techniques and their applications
in the field of Physical Chemistry. You will learn principle, instrumentation and also have
hands on laboratory experience on operation of instruments, collection of data and analysis.
You will be introduced to operation and applications of FTIR spectrophotometer, UV-vis
spectrophotometer, cyclic voltammetry, photoluminescence spectrophotometer, BET surface
area analyzer for both qualitative and quantitative analysis. In addition to the experimental
work you will also learn about computer-aided drug discovery and computational chemistry.
Best Practices in the Laboratory:
1. Enter the laboratory with your Labcoat. This is for your safety.
2. Read this instruction manual before coming to the laboratory.
3. Each experiment will be carried out on a specified work bench. All chemicals and
instruments are placed, as per experiment, on the work bench. DO NOT misplace them.
4. Standard solutions are kept in the working areas and additional chemicals can be issued
by the concerned person, when required.
5. Handle flammable and poisonous materials in the hood.
6. Keep your work area clean, handle the equipment carefully.
7. Inform the instructor if any apparatus becomes defective, or breakage occurs.
How to Prepare Reports:
A report should concisely describe in your own words the experiment so that you can
easily follow the objectives of the work. Use secondary literature and do not simply copy from
textbook/instruction manual. The purpose and results of the experiment should be clearly
mentioned. All pages must be numbered. Do not overwrite in your notebook. False entries
should be crossed out but still remain legible. Figures should be generated by computer or
produced using appropriate graph paper.
The following guidelines should be used:
1. The Lab record must have your name, admission no, date of experiment and date of
submission, with a clear index and page number.
2. The lab record must be written under following headings:
a. Title: name and number of experiment.
b. Aim of Experiment: a short introduction as to what is to be investigated and
how it is to be carried out.
c. Theory: describe concisely, in your own words, the theoretical background, the
purpose of the experiment. Equations must be numbered and all symbols must
be defined.
d. Apparatus and Chemical Required: Note down the chemicals and instruments
required for the experiment.
e. Procedure: Describe in your own language the experimental procedures.
f. Experimental Results: set up neat, concise, and carefully thought-out tables
before lab time, ready to use for recording experimental data in the laboratory.
Column headings should contain the name of the quantity, the internationally
accepted symbol, and the dimensions (for example, Temperature T K). All data

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 must be entered in the notebook as you obtain it. Use a small copy for your data
and then transfer it, after appropriate modifications, to your notebook.
g. Calculations and Error: refer to equations, tables, and graphs by consecutive
numbers. Define all symbols when you introduce them. Each equation should
be part of a sentence. Give a ‘typical sample calculation' to illustrate how you
did it. Error analysis will depend on the experimental procedure. A typical error
calculation should include: determination of standard deviations for 3 or more
determinations of the same quantity and propagation of errors.
h. Conclusions: Briefly summarize the results and conclusions of your paper.

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Laboratory Safety Guideline
Common safety practice and guidelines must be obeyed at all times when you are in the
laboratory. When unsure on any matter related to safety, seek help from the lab-in-
charge/Instructor. The basic guidelines are as follows.
1. Lab coats must be wear in the laboratory at all times. Long hair must be tied back. No
loose or baggy clothes. Proper attire must always be wear in the laboratories, including
shoes that completely cover the foot (no high-heeled shoes).
2. Safety eyewear must always be worn during laboratory sessions.
3. Prior to handling any chemical, please make sure you have read its Safety Data Sheet
(SDS).
4. DO NOT dispose organic solvent into the sink. Any used organic solvent must be
transferred into the appropriately labelled waste bottles. Please consult the lab assistant
if you are uncertain.
5. When dealing with high pressure or high voltage equipment, please read and understand
the instruction thoroughly before proceeding with the experiment.
6. Be organized. Maintain a clean, open work area free of anything except materials
directly required for the exercise. Keep laboratory material/equipment away from edges
of work surfaces and electrical cords from hanging below the surface of tables.
7. Equipment and/or chemicals should never be taken out of the lab unless authorized by
the instructor or laboratory staff.
8. Be familiar with the location and the use of the following in your laboratory: e.g. broken
glass receptacle, first-aid kit, emergency gas shut-off valves, closest fire alarm, fire
extinguisher, eye wash, safety shower, and emergency exit and routes.
9. Be prepared. Study the assigned experiment before you come to lab. Be familiar with
the lab exercise to prevent confusion and accidents. No unauthorized experiments are
to be performed. Students must follow the procedural instructions in the lab
handout/manual unless modifications to the procedures have been announced by the
laboratory in-charge, in which case the student must follow the supervisor’s procedural
instructions.
10. NEVER TOUCH ANY FORM OF BROKEN GLASS. Broken glass should be
disposed of only by laboratory staff.
11. Smoking, eating, and/or drinking are prohibited in the laboratories.
12. Other hazards specific to a particular experiment are described in the textbook.
13. No student is permitted to work in the laboratory without the supervision of an
instructor. If for exceptional reasons you have to work during some other physical
chemistry lab section, you must have the permission of your instructor and the
corresponding instructor in charge.
14. You will be penalized for any breakage of glassware as well as mishandling of
instruments

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 Experiment 1

Calculation of Photoluminescence Quantum Yield (PLQY)

Aim: To determine the quantum yield of unknown sample.

Apparatus: 100 ml beaker, Micropipette, UV-Vis spectrophotometer, PL
spectrophotometer.
Chemical required: Rhodamine 6G, Fluorescein, Quinine sulphate and ethanol.
Theory: The fluorescence quantum yield is defined as the ratio of the number of photons
emitted to the number of photons absorbed. Experimentally, relative fluorescence quantum
yields can be determined by measuring fluorescence of a fluorophore of known quantum
yield.
𝑵𝒐.𝒐𝒇 𝒑𝒉𝒐𝒕𝒐𝒏𝒔 𝒆𝒎𝒊𝒕𝒕𝒆𝒅
𝚽 = 𝑵𝒐.𝒐𝒇 𝒑𝒉𝒐𝒕𝒐𝒏𝒔 𝒂𝒃𝒔𝒐𝒓𝒃𝒆𝒅…………………………….. 1

There are two methods for calculating the fluorescence quantum yield – single point
and comparative. The comparative method involves the creation of a calibration curve using
multiple standards of a compound with known fluorescence quantum yield. Plotting the area
of fluorescence against the absorbance for different concentrations of the fluorophore, this
method provides high accuracy by calculating the slope of the line generated. The PLQY is
calculated by the relative method with the given formula.
𝑄𝑈 = 𝑄𝑅 . 𝑚𝑈 ⁄𝑚𝑅 . 𝜂𝑈2 ⁄𝜂𝑅2 ………………………….. 2
Where, “Q” signifies quantum yield, “m” indicates slope, and “η” as the refractive index.
The subscript “U” and “R” represents the given fluorophore and their corresponding
references. The references can be different dyes like Rhodamine 6G, Fluorescein, Quinine
sulphate, etc.
General Experimental Considerations:
Standard samples. The standard samples should be chosen to ensure they absorb at the
excitation wavelength of choice for the test sample, and, if possible, emit in a similar region to
the test sample. The standard samples must be well characterized and suitable for such use.
Cuvettes. Standard 10 mm path length fluorescence cuvettes are sufficient for running the
fluorescence measurements. In order to minimize errors in calculating the absorbance of each
solution, it is advisable to use absorption cuvettes with extended path lengths (for example, 20
mm, 50 mm).
Sample preparation. It is vital that all glassware is kept scrupulously clean, and solvents
must be of spectroscopic grade and checked for background fluorescence.
Procedure:
1. Record the UV-vis absorbance spectrum of the solvent background for the chosen sample.
Note down the absorbance at the excitation wavelength to be used.

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2. Record the fluorescence spectrum of the same solution in the 10 mm fluorescence cuvette.
Calculate and note down the integrated fluorescence intensity (that is, the area of the
fluorescence spectrum) from the fully corrected fluorescence spectrum.
3. Repeat steps 1. and 2. for five solutions with increasing concentrations of the chosen
sample.
(There will be six solutions in all, corresponding to absorbance at the excitation wavelength
of ~0/solvent blank, 0.02, 0.04, 0.06, 0.08 and 0.10.)
4. Plot a graph of integrated fluorescence intensity vs absorbance. The result should be a
Straight line with gradient m, and intercept = 0.
5. Repeat steps 1. to 4. for the remaining samples.
Observation:
Table: Integrated PL intensity vs. absorbance plot.
Sl.no. UV-visible absorbance Area of PL spectra (U) Area of PL spectra (R)
1.
2.
3.
4.
5.

Calculation:
 The slope of reference and sample can be achieved by plotting the graph between
integrated fluorescence intensity and absorbance.
 Put the slope value and other value in equation 2.

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 Fig.1 linear plot s for two standard samples.

Result:
The fluorescence quantum yield is ……………………

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 Experiment 2

Synthesis of fluorescent carbon quantum dots from lemon juice and study
of its optical property

Aim: Synthesis of fluorescent carbon quantum dots from lemon juice and study of its optical
property.

Apparatus: 100 ml beaker, Teflon-lined stainless-steel autoclave, UV-Vis spectrophotometer,

PL spectrophotometer.

Chemical required: Pulp free lemon juice and ethanol.

Theory:

Carbon dots are nanoparticles of nanometer size (less than 10 nm but can be as small as 1 nm)
which have been first discovered during purification of single-walled carbon nanotubes.
Carbon dots (CDs) have emerged as promising candidates for replacing traditional
semiconductor quantum dots and organic dyes because of inexpensive carbon sources, facile
synthetic routes, unique physical properties, and extremely low toxicity. A vast number of
carbon sources and synthetic methods have been developed to produce CDs for a wide range
of applications, such as bioimaging, sensing, catalysis, full color displays, and optoelectronic
devices.

Lemon juice, as a very common and inexpensive drink, contains vitamins, minerals and
carbohydrates necessary for CD synthesis. Here, we will use pulp free lemon juice as carbon
precursor for the synthesis of CDs. The optical properties are checked by UV-visible and
fluorescent spectroscopy.

Fig. 2 (a) UV-Vis spectra and PL spectra of synthesized carbon dots.

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Synthesis of CDs:

1. Make a transparent solution by adding 20 mL of pulp-free lemon juice with 10 mL of ethanol.

2. After that, transfer the mixture into a 100 ml Teflon-lined stainless-steel autoclave and heat
at 190 °C for 10 hours.

3. After cooling the autoclave naturally, check the UV-visible absorbance and fluorescence
spectra.

Result:

1. The synthesized CDs have ……………….color under UV light.

2. The λmax of UV-visible absorbance is …………… nm.

3.. The fluorescence spectra have excitation spectra at ……………..nm with maximum
emission at …………….nm.

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 Experiment 3

Spectroscopic determination of Critical Micelle Concentration

Aim: To determine the CMC of a surfactant by fluorometric method.

Apparatus Required: volumetric flasks, glass vials, pipettes and PL spectrophotometer.
Chemicals Required: Sodium dodecyl sulphate (SDS), Coumarin-6, and DCM.
Principle: Surfactants are the molecules which get adsorbed at an interface and thus alters the
surface tension. Above a certain concentration these molecules aggregate to form micelles and
this concentration is known as critical micelle concentration (cmc).
Around the CMC, the properties of the solution show sharp changes that can be detected by
various methods. Here, we will use fluorescent probe or dye micellization method for CMC
detection. It relies on a change in fluorescence intensity emission from the dye after micelle
self-assemble. The fluorescent probes can be classified into two types. Fluorescent turn-off
probes show almost no emission in solutions but strong emission in micelles, and fluorescent
turn-on probes show strong fluorescence in solution but very weak emission in micelles. Dyes
such as sudan, coumarin, rhodamine, pyrene and eosin are all suitable as turn-off probes due
to a shift in the wavelength maximum when increasing the surfactant concentration, and
consequently, an increase in dye solubility. However, these peak shift methods, like in the case
of the most commonly used pyrene assay, are limited by inaccuracy and inadequate
reproducibility.
Procedure:
1. Prepare a stock solution of 6 μM coumarin-6 in DCM.
2. Add approximately 40 μl stock solution to an empty glass vial and left for 30 minutes to
evaporate the solvent.
3. Prepare different concentration of SDS, ranging from none to twice the CMC value reported
in literature.
4. After that, transfer 400 μl each tested solution to the vial containing the solvent evaporated
fluorescent dye.
5. After 15 minutes of sonication, analyze the fluorescence spectra of each test solution.

Treatment of Results:

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 Conc. (μl)

FL. Intensity

Plot the graph with fluorescence intensity value against logarithm of SDS concentration. A
graph consisting of two straight lines will be obtained. Extrapolate the lines and find the point
of intersection gives the critical micelle concentration of SDS.

Result: Report the critical micelle concentration value of the surfactant, sodium dodecyl
sulphate at the experimental temperature.

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 Experiment 4

Functional group determination of surface modified nanoparticles using IR

spectroscopy
Aim: Determination of the infrared spectrum and functional groups of the given sample.
Theory
We will study several alcohols, alkenes, aldehydes, amines, and ketones using IR spectroscopy
to understand the functional groups present in these compounds respectively. For example, all
alcohols contain a 'O-H' group attached to a sp3 hybridized carbon atom. Alkenes contain a
carbon-carbon double bond (C=C), and ketones contain a carbon-oxygen double bond (C=O).
IR may be thought of as a Functional Group detector. The quickest and easiest way to determine
the presence of one of these "Functional Groups" is to take the IR spectrum of the compound.
The technique is simple and can often provide a definitive answer in less than ten minutes.
Evidence provided by IR is widely respected. It is commonly used in judicial proceedings as
much as fingerprints are used. In fact, the IR of a pure compound bears the same relationship
to that compound as fingerprints do to an individual.

Instrumentation

A IR instrument consists of a IR light source, a sample holder, a means of selecting individual

wavelengths or frequencies of the light, some means of detecting the amount of incident light
that the sample absorbs, and a device for plotting the amount of light absorbed as a function of
wavelength or frequency. This plot is referred to as the 'IR Spectrum.' Since IR light is absorbed
by most materials, the optics of an IR Spectrophotometer requires special materials. Most
frequently they are built of NaCl or KBr — water soluble salts. This requires that the IR
spectrophotometers be protected from moisture of any form. The instrument is usually sealed,
but the windows, and the sampling devices require special handling. Aqueous samples should
never be used, and the sample holders must be cleaned with DRY organic solvents like reagent
grade acetone.

Sampling

IR spectra can be determined for solids, liquids, or gases. IR gas analysis is a common
analytical tool for those involved in studies of atmospheric pollution. The only drawback is
that it is very expensive and delicate cells are needed. IR spectra of solids and liquids are
usually obtained by dissolving the sample in a relatively IR transparent solvent such as
CCl4 and using simple liquid cells. A solid could also be ground to a fine paste with NUJOL (a

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mixture of highly purified hydrocarbons) and the resulting 'mull' studied directly. The NUJOL
exhibits only a very few well defined peaks that can be ignored when examining the spectrum
of the mull. Solid spectra may also be obtained by mixing the solid with dry KBr, grinding to
a fine, well mixed powder, and then forming a disk of the mixture by applying high pressure
in a specially designed device. The resulting 'KBr Disk' will produce a spectrum free of almost
all extraneous peaks. Liquids are the easiest to study by IR. A pure sample of the liquid (1-2
drops) may be placed between two disks of pure NaCl or KBr and the resulting 'sandwich'
placed directly in the sample holder of the spectrometer. Excellent spectra can be obtained in
a matter of a few minutes with minimum expense. This technique is called running
a "neat" spectrum, meaning the spectrum is of the pure liquid only, without solvent.

Procedure:
Step 1. Make a fresh KBr Pellet using pelletizer.

Step 2. With a Pasteur pipet, add about 2 drops of your dry liquid sample to the centre of one
face of a clean, dry salt (KBr) plate. Press a second dry salt plate onto the first to make a
"sandwich" of your sample. Hold the plates up and look to see that the liquid has evenly spread
between the plates. If there is an uneven film between the plates, take them apart and clean
them with a clean. Begin again, using one or at most two more drops than before.
Step3.
Once you have a clear "sandwich," it may be placed in the SAMPLE beam of the
spectrophotometer.
Step 4.
Take your spectrum, print it, and record on it the wavelength of significant peaks (the most
prominent peaks in the spectrum).
Step 5.
Remove the plates from the IR instrument, separate the salt plates, rinse them with dry acetone,
dry them with a clean Kimwipe, and return them to the desiccator.
Step 6.
On your spectrum, record the sample name, date, your name, and other relevant
information. Make sure your TA inspects and approves your spectrum before you consider it
finished and turn it in with your worksheet.

Observation:
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Compare the spectrum of your compound with the spectra of the compounds in the functional
group that you have circled with the reference spectra. Identifying other major peaks may help
you isolate the compound. Write the name of the Functional groups you believe your unknown
to be. Here you will be synthesized Poly(vinylpyrrolidone)-Modified Zinc Oxide
Nanoparticles.

Synthesis of ZnO Nanoparticles using Solid State Reaction Method

0.2M of Zinc acetate dihydrate in methanol was first ground for by mortar pestle for 10 min

and then mixed with 0.02M of NaOH. After the above mixture was ground for 30 min, the

product was washed many times with deionized water. After that the product was again washed

with methanol to remove the by-products. The final product was then filtered using micron

filter paper and dried into solid powder at 80ºC for 15 min on hot plate. After that the powder

was annealed at 400ºC for 30 min.

Synthesis of PVP-Modified ZnO Nanoparticles.

500mg of ZnO Nanoparticles was mixed in 25ml of water followed by continuous shaking for

15min. After that, 750 mg of PVP was added in the resulting solution and shake for another

15min. The final product was filtered using filter paper and dried at 100ºC.

Result:
The functional group present in the given sample are ………

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 Experiment 5
Estimation of band-gap for Cu nanoparticles using absorption spectroscopy
Aim: Synthesis and optical properties determination of copper nanoparticles prepared by a
chemical reduction method.

Theory: Copper nanoparticles, due to their interesting properties, low cost preparation and
many potential applications, cooling fluid or conductive inks, have attracted a lot of interest in
recent years. The copper nanoparticles are synthesized through the chemical reduction of
copper sulfate with sodium borohydride. The UV–vis spectrometry is used to study the optical
properties of the nanoparticles. The surface plasmon resonance phenomenon are related to the
change in particle size. The surface plasmon resonance peak shifts from 561 to 572 nm, while
the apparent color changes from red to black. The color of the solution changes from red to
violet and ultimately a blue solution appears upon oxidation. The optical band gap is measured
via indirect band gap calculation. The UV-Vis absorption spectrum calculation was processed
by plotting √𝐴ℎ𝑣 versus hν, where A is the measured absorbance, h is the Plank constant, ν is
the frequency, and hν is equal to 1240/wavelength in unit of eV. √𝐴ℎ𝑣 has a linear relationship
with hν with a slope of D and the optical band gap is the x-intercept.

Procedure:

Step1: Dissolve copper (II) sulfate pentahydrate salt, CuSO4 · 5H2O (0.01 M), in deionized
water to obtain a blue solution.

Step2: Next, dissolve polyethylene glycol 6000, PEG 6000 (0.02M) in water and add this to
the aqueous solution containing the copper salt with vigorous stirring.

Step 3: Then, dissolve ascorbic acid (0.02 M) and sodium hydroxide (0.1 M) in water and add
it to the synthesis solution.

Step 4: Finally, prepare a solution of NaBH4 (0.1 M) in deionized water and add to the solution
under continuous rapid stirring. An instant color change will occur in the aqueous phase from
yellow to black/red. The appearance of dark color indicates that the reduction reaction has
started. Further, stir the mixture rapidly for around 10 min in ambient atmosphere, to allow the
reaction to complete.

Observation:

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Table. Plasmon resonance after synthesis and qualitative stability duration as a function of
reaction time during synthesis.

.Sample Reaction time of soln. (min) λmax(nm) Color Stability time

1.
2.
3.
4.
5.

Graph:

To calculate the band gap, plot the graph between √𝐴ℎ𝑣 vs hv.

√𝐴ℎ𝑣

hv (eV)
Result:
1. The presence of the surface plasmon resonance on these nanoparticles
………………..
2. The calculated band gap is ………………..

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 Experiment 6

Effect of extended conjugation on the wavelength of maximum absorption of

organic compounds.
Aim: Study on the effect of extended conjugation on the wavelength of maximum absorption
of organic compounds.
Theory: In most cases, the reason for the color is tied to one phenomenon in organic
compounds: conjugation. Conjugation is a specific pattern in the electronic arrangement of
molecules. A Lewis structure of a conjugated molecule shows alternating single and double
bonds between carbon atoms. It turns out that conjugation has a very predictable effect on the
energy levels of the electrons involved in those alternating bonds. It smears out the energy
levels. Some of them are pushed a little higher in energy. Some drop a little lower. Many of
them become spread out in between. As a result, the gaps between those energy levels becomes
smaller and smaller as the amount of conjugation increases in a molecule.

Because longer frequency = smaller energy, this means that the energy gap ΔE between
the highest-occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital
(LUMO) decreases as the number of conjugated pi bonds increases.

For example, benzoic acid shows primary band at 250 nm and secondary band at 273 nm, but
cinnamic acid that has longer chromophore exhibits primary band at 273 nm and secondary
band remains merged with it. Similarly, in benzaldehyde, the secondary band appears at 282
nm and primary band at 242 nm but in case of cinnamaldehyde, primary band appears at 281
nm and remains merged with secondary band. The hyperchromic effect arising due to extended
conjugation is also visible.

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Procedure:
1. Take the diluted benzaldehyde and cinnamaldehyde.
2. Scan the UV-vis absorbance plot.
3. Compare the maximum absorbance (λmax) of these organic compounds.
Result:
The λmax of benzaldehyde and cinnamaldehyde is ……….. and…………..nm.

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 Experiment 7

Determination of thermodynamic parameters for the reaction by EMF

method.
Aim: To determine the thermodynamic parameters ΔG, ΔS and ΔH for a reaction by EMF
measurements.

Apparatus Required: Potentiometer assembly, H shaped cell with zinc amalgam and silver
chloride solution.

Chemicals Required: 0.1M ZnCl2, 0.001M HCl.

Principle: The net electrical work performed by a reaction yielding an EMF and supplying a
quantity of electricity Q is Q × E. For each equivalent reacting, Q is equal to the Faraday F and
hence for n equivalents reacting Q = nF. Therefore, the electrical work obtained from my
reaction supplying nF coulombs of electricity at a potential E is,

Net electrical work = nFE

But any work performed by a cell can be accomplished only at the expense of a decrease
in free energy occurring within the cell. Further, when the electrical work is a maximum, as
when the cell operates reversibly, the decrease in free energy, ̵ ΔG, must equal the electrical
work done. We obtain therefore, ΔG = ̵ nFE from which we see that the reversible EMF of any
cell is determined by the free energy change of the reaction going on in a cell. This equation is
the bridge between thermodynamics and electrochemistry. Through it the evaluation of various
thermodynamic functions of reactions becomes possible from EMF measurements.

Procedure: Standardize the potentiometer. Place the H-shaped cell with Zn(Hg) electrode in
one limb, the Ag/AgCl electrode in the other and the ZnCl2 + HCl solution as the common
electrolyte in the thermostat. Find out the cell EMF corresponding to the constant temperature
of the water bath. Vary the temperature and find out the EMF of the cell at different constant
temperatures.

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Treatment and Results:
Record the EMF measured at different temperatures in the following table.
Temperature (̊C) EMF in volts ΔH in kJ ΔS in J ΔG in kJ

1. Plot EMF against temperature and obtain the slope;

Slope = (δE/δT)P = ……… volt/deg

2. Calculate ΔH and ΔS for the reaction

Zn + 2AgCl → ZnCl2 + 2Ag
from the following relationships
ΔS = nF (δE/δT)P, ΔG = – nFE
ΔH = - nF [E – T (δE/δT)P]
Where n = 2; F = 96500 coulombs.
Results:
1. Report the temperature coefficient of EMF.
2. Report the values of the thermodynamic functions, ΔG, ΔH and ΔS.

Note:
The change in the free energy, ΔG for any process is related to the change in heat content, ΔH
by Gibbs-Helmholtz equation
ΔG – ΔH = T {d(ΔE)/dT}P (1)
If the equation, ΔG = – nFE (2)
If differentiated with respected to temperature then
{d(ΔE)/dT} = – nF (dE/dT)P (3)
and on substituting equations (2) and (3) into equation (1) we find
– nFE – ΔH = – nFE (dE/dT)P
ΔH = – nFE + nFT (dE/dT)P
= nF (dE/dT)P – E]J (4)
Equation (4) permits the calculation of the heat of a reaction from the measured EMF
and temperature coefficient of EMF of the reaction, or (dE/dT)P is obtained from ΔH and E. In
this equation ΔH is in joules if E and F area in volts and coulombs respectively, while ΔH must
be substituted in joules to obtain E in volts or (dE/dT)P or in view of equation (3)
ΔG – ΔH = – nFT (dE/dT)P (5)

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 Therefore, for an electrochemical reduction ΔG can equal ΔH only when (dE/dT)P = 0.
Further,
ΔG = ΔH – T ΔS (6)
Comparison of equations (5) and (6) yields
– T ΔS = – nFT (dE/dT)P
and ΔS = nF (dE/dT)P

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 Experiment 8

Determination of the surface area of silica by N2 adsorption at 77K.

Aim: Determination of the surface area of silica by N2 adsorption at 77K.

Theory: The determination of specific surface areas represents a major task regarding the
characterization of porous and finely-dispersed solids. If a gas gets in contact with a solid
material a part of the dosed gas molecules is being adsorbed onto the surface of this material.
The adsorbed amount of gas depends on the gas pressure, the temperature, the kind of gas and
the size of the surface area. After choosing the measuring gas and temperature, the specific
surface area of a solid material can be reliably and comparably calculated from the adsorption
isotherm. Due to practical reasons the adsorption of Nitrogen at a temperature of 77 K (liquid
Nitrogen) has been established as the method for the determination of specific surface areas.
Stoeber silica particles serve as a model adsorbent because of the regular spherical shape of the
particles of uniform size. It has been established that Stoeber silica has a microporous structure.
Procedure;
Silica particles will be prepared by the method of Stober. A mixture of 0.79 M NH3, 14.4 M
H2O, and 46.5 vol % ethanol stirred and held at 40 °C to get the hydrolysis product of silica
by 0.2 M TEOS (tetraethyl orthosilicate). The addition of TEOS will be controlled in a way
that the temperature of the mixture did not rise above 45 °C. Stirring was continued during 30
min. The suspension of the silica particles purified and concentrated by distillation at 77-80 °C.
After distillation, the slurry washed with deionized water, filtered through a Millipore filter of
pore size of 0.22 μm several times, and then dried in an oven at 120 °C overnight.
Analysis method
Speaking about the BET method, actually means the analysis of isotherm data by a method
developed by Brunauer, Emmett and Teller. By means of the BET equation the amount of
adsorbed gas, which build up one monolayer on the surface, can be calculated from the
measured isotherm. The amount of molecules in this monolayer multiplied by the required
space of one molecule gives the BET surface area. Besides the adsorption of Nitrogen at 77 K,
Krypton adsorption at 77 K is recommended for the determination of very small surface areas.

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 Figure: Adsorption isotherm of N at 77K on Stober silica
Result:
The surface area of silica is ………………….

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 Experiment 9

Precipitation titration and determination of solubility of a sparingly soluble salt

Aim: Determination of solubility of a sparingly soluble salt
Introduction: Many metal salts dissolve in water to some degree, to produce hydrated
positive and negative ions. Up to a certain concentration, referred to casually as the
solubility, the salt will completely dissolve; after this point, any further salt that is added
will not apparently dissolve and the solution is said to be saturated.
In this experiment, we will measure the solubility of a slightly soluble salt, lithium
carbonate. This compound is used to treat manic depression and bipolar disorder; although
non‐ toxic, it should be handled with care. The solubility of this salt changes slightly with
temperature, so the filtration of the saturated solution is performed at a fixed temperature.
An alternative way to describe solubility is in terms of the solubility product constant
orKSP. In this description, the solid form is described as being in equilibrium (balance)
with the dissolved (hydrated) form. If there is more salt present than can dissolve in the
given amount of water, we can say that the amount of solid dissolving is equal to the amount
of dissolved salt that is precipitating.
The dissolved form is present as positive and negative ions, and the solubility product
constant is based upon the concentration of these ions. For a simple 1:1 salt such as lithium
fluoride (LiF), the KSP value is equal to the concentration of Li+ times the concentration of
F−, written as:
KSP = [Li+] [F−]
The square brackets mean “molar concentration of whatever is within the brackets." With
lithium carbonate, the situation is more complicated, because we have two lithium ions for
2−
one carbonate. Therefore, we use this equation: KSP = [Li+]2 [CO3 ]
In this experiment, you will measure the solubility of lithium carbonate. This is done by
performing an acid‐ base titration on a saturated solution to measure the concentration of
lithium carbonate present, = [Li2CO3]. From this, you can calculate the KSP. The equation
for the titration is:
Li2CO3 (aq) + 2 HCl (aq) 2 LiCl (aq) + H2O (l) + CO2 (g)
Materials
2 g Li2CO3, 100 mL distilled water, Methyl orange indicator, Approximately 100mL of 0.3
MHCl, pH indicator paper.
Procedure:
1. Weigh approximately 2 g lithium carbonate, and add this to 100 mL room
temperaturedistilled water. Record the mass of Li2CO3 used in the data table on the next
page.
2. Set the cloudy mixture to stir for 15‐ 20 minutes on a magnetic stirplate, or swirl by
hand.You will have some solid material that will not dissolve.
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3. Filter the mixture at room temperature using simple gravity filtration, collecting the filtrate
in a 150 or 200 ml beaker. The liquid portion (the "filtrate") is the saturated solution you will
test.
4. Measure 25 mL of this saturated Li2CO3 solution and dispense this into a 250 mL
Erlenmeyer flask. Add two drops of methyl orange indicator.
5. Titrate the solution against 0.3 M hydrochloric acid (around 30 mL will be needed). Note
the exact concentration of HCl. At the endpoint, the indicator should turn from yellow to
orange‐ red. Record the volume of HCl used for each titration in the data table on the next page.
6. Carry out the titration two more times, recording the data from each titration in the data
table.
7. After titration, the orange‐ red solutions can be mixed with the leftover lithium carbonate
and washed directly down the drain with water. Check the pH of the solution with pH paper
before washing down the drain. It should be a pH of 6 – 8. If necessary, add more acid and
swirl to neutralize the solution until an appropriate pH is reached.
Mass of lithium carbonate used (g)
Exact HCl concentration (mol/L)

Titration Number Vol final (mL) Vol initial (mL) Vol delivered = Vf – Vi
1.
2.
3.
Calculations:
Fill out the table below, by carrying out the calculations shown underneath.
Vol of HCl Vol of HCl Vol of HCl Vol of HCl Vol of HCl Vol of HCl
(A) (B) (C) (D) (E) (F)

A. Calculate the number of moles of HCl in each titration, from the volume used in each
titration:

B. Calculate the number of moles lithium carbonate present in 25 mL, using the number
of moles HCl used in each titration. Since one mole of Li2CO3 reacts with two moles of HCl,
the number of moles of Li2CO3 is simply half the number of moles of HCl.

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26 | P a g e
C. Calculate the molarity of lithium carbonate or, which is the number of moles of lithium
carbonate present in 1000 mL, from the amount present in 25 mL (B):

D. Calculate [Li+]
2−
[Li+] = 2[CO
3 ] = 2[Li
2 CO
3 ]

E. Calculate KSP of Li2CO3. This should be a very small number.

Conclusions:
1. Calculate the average value for the KSP of lithium carbonate at 20°C.
2. Use a reference book or on‐ line sources to find the actual Ksp of lithium carbonate.
3. Calculate the % error of your calculated Ksp of lithium carbonate.
4. Discuss possible sources of error that would account for a discrepancy of greater than 10%.
 Experiment 10
Determination of the concentration of a given solution using Cyclic Voltammetry

Aim: Determination of the unknown concentration of K3[Fe(CN)6] with 1M KCl solution using
Cyclic Voltammetry
Theory: Cyclic voltammetry (CV) is a technique used to study reaction mechanisms that involve
the transferring of electrons. The method involves linearly varying an electrode potential between
two limits at a specific rate while monitoring the current that develops in an electrochemical cell.
Although CV is best at providing qualitative information about reaction mechanisms, several
quantitative properties of the charge transfer reaction can also be determined. Cyclic voltammetry
involves applying a voltage to an electrode immersed in an electrolyte solution, and seeing how
the system responds. In CV, a linear sweeping voltage is applied to an aqueous solution containing
the compound of interest. A linear sweeping voltage is defined by the voltage being varied linearly
at the speed of the scan rate. Cyclic voltammetry generally uses a 3 electrode configuration. The
electrodes are a working electrode, a reference electrode, and a counter electrode. The working
electrode can be seen as a medium whose reductive or oxidative power can be externally adjusted
by the magnitude of the applied potential. As the potential is increased or decreased linearly versus
time, the working electrode becomes a stronger oxidant or reductant, respectively. Therefore, the
working electrode, which typically consists of a chemically inert conductive material such as
Platinum or Graphite, acts as a donor or acceptor of electrons. The reference electrode, typically
AgCl or calomel, keeps the potential between itself and the working electrode constant. The
potential is measured between the reference and working electrodes, and the current is measured
between the working and counter electrodes. A counter electrode (typically Platinum wire or strip)
is employed to allow for accurate measurements to be made between the working and reference
electrodes. The counter electrode's role is to ensure that the current does not run through the
reference electrode since such a flow would change the reference electrodes potential. The
resulting reversible cyclic voltammogram from a typical potential against time profile is shown in
the following Figure 1.
 Figure 1. Cyclic Voltammogram of measured current versus applied potential. This diagram
also shows the points where the y-values of peak anodic current (ipa) and peak cathodic current
(ipc) as well as the x-values of peak anodic potential (Epa) and peak cathodic potential (Epc).
The peak current in a cyclic voltammogram containing only one species is described by:
ip = (2.69 × 105) n3/2 S DA1/2 V1/2 CA
Variable Description Units
ip peak current A
n number of electrons transferred -
S Surface Area of electrode cm2
DA Diffusion coefficient cm2/s
 scan rate V/s
CA the concentration of compound A in the bulk solution mole/cm3
Thus for a given redox active solution if all the other parameters are known, then from the
peak current the concentration of unknown solution can be calculated.
Procedure:
 Prepare a solution of 0.005 (M) K3[Fe(CN)6] with a supporting electrolyte (KCl) of
concentration 1(M).
 Place the working electrode, the Ag/AgCl reference electrode, and the platinum counter
electrode in the solution.
 Run CV for the above electrolyte in potential range -0.1 to 0.5 V at scan rates of 30, 100
and 300 mV/s.
 Collect and Plot the CV voltammogram note down peak current..
 Calculate diffusion coefficients for different scan rates and average out.
 Clean the electrodes with distilled water thoroughly.
 Place the electrodes in the unknown solution.
  Run CV in potential range -0.1 to 0.5 V at a fixed scan rate.
 Collect and Plot the CV voltammogram note down peak current.
 Calculate concentration and report.
Representative plot for calculation of diffusion co-efficient.

Calculation:
ip = (2.69 × 105) n3/2 S DA1/2 V1/2 CA

=>
For ferricyanide system: n=1
Calculate diffusion co-efficient for the three scan rates and average out to get DA.
For unknown solution:
Note down ip from the CV plot and calculate CA
Conclusion: Report the concentration of the unknown solution.
 Experiment 11

Potential Energy Surface Calculation

Objective: To calculate the 1D potential energy surface for rotation around a dihedral
angle of a molecule

Software Used: Gaussian09, Gauss view, xmgrace

Theory: Gaussian09 is a computer program used by chemists, chemical engineers, biochemists,

physicists, and others. It utilizes Quantum Mechanics methods to predict energies, molecular
structures, spectroscopic data (NMR, IR, UV, etc), and much more. Quantum Mechanics is
governed by the Schrödinger equation (SE) which is a linear partial differential equation that
governs the wave function of a quantum-mechanical system.

Under Born-Oppenheimer approximation, the nuclear motion of the molecules is assumed to be

zero and only electronic motion is considered, giving rise to electronic SE which is solved using
the Gaussian09 software.
There are mainly two ways of solving electronic SE:
1. Hartree-Fock (HF) methods:
HF is one of the simplest approximate theories for solving the many-body Hamiltonian. It
is based on a simple approximation to the true many-body wavefunction: that the
wavefunction is given by a single Slater determinant of N spin-orbitals. Moreover, the
wavefunction is antisymmetric with respect to an interchange of any two-electron
positions.
2. Density Functional Theory (DFT): Instead of the many-body wave function, the one-
body electron density is used as the fundamental variable. Since the density n(r) is a
function of only three spatial coordinates (rather than the 3N coordinates of the wave
function), DFT is computationally feasible even for large systems. The whole density-
based method is formally described using Hohenberg–Kohn theorems.

Basis set: A basis set in theoretical and computational chemistry is a set of functions that is used
to represent the electronic wave function in the HF method or DFT in order to turn the partial
differential equations of the model into algebraic equations suitable for efficient implementation
on a computer.
STO-3G basis set are minimal basis sets, where 3 primitive Gaussian orbitals are fitted to a
single Slater-type orbital (STO).

6-31G basis set is split-valence double-zeta basis set core orbital is a Contracted Gaussian-Type
Orbitals (CGTO) made of 6 Gaussians, and the valence is described by two orbitals — one
CGTO made of 3 Gaussians, and one single Gaussian. In genral 6-31G basis set is more accurate
than STO-3G basis set.

Figure 1. Anatomy of a Basis Set: C atom, 6-31G

Conformational isomerism is a form of stereoisomerism in which the isomers can be

interconverted just by rotations about formally single bonds (Figure 2).
Figure 2. Rotation about a single bond of butane to interconvert one conformation to another. A
represents anti/trans conformation and D represent cis conformation. The gauche conformation is
represented by B, while the eclipsed conformation (C) is a transition state between conformers A
and B.
It is expected that a molecule’s most stable conformation is where the largest electronegative
groups are anti to each other, minimizing the destabilizing effect of electrostatic repulsion between
them. Other stable conformations include gauche positions.

Procedure:
1. Open the gaussview software on the system.
2. Go to File-> New -> create new molecule group.
3. Build a trans n-butane molecule in the newly open window. Right click on the same
window and turn on view -> labels. Record the atom numbers of the carbon atoms
required for defining the dihedral.
4. Right click on the window containing n-butane structure. Go to Edit -> Redundant
coordinates
5. Click on Add button and add dihedral details for scan coordinate option. A 360° scan will
be performed by taking 24 steps of 15° each (Figure 3). After this close the Redundant
coordinate window.
6. Go to calculation -> Gaussian calculation setup and in methods dialog select Hartree-
Fock method and basis set as STO-3G. Additionally one can go to Link0 to set the
required CPU number and memory required for the job. A sample input file is shown in
Figure 4.
7. Click submit and save the file as job1.com & run the job.
8. After job is complete, open the logfile, right click on the workspace and go to Results->
scan. Save the plot shown.
9. Repeat the same computation using 6-31G basis set for n-butane and STO-3G & 6-31G
basis set for n-pentane.
 Figure 3. Redundant molecular editor with settings.

Figure 4. Sample input file for Gaussian scan job

Observations:
Plots of scan results (i.e. dihedral angles vs energy) for all 4 jobs.
Identify the regions for all the conformational isomers.
Report the following energy values in kcal/mol (conversion factor 1 hartree = 627.51 kcal/mol):

System Basis Set E(anti) E(eclipsed) E(gauche) E(cis)

n-Butane STO-3G
6-31G
n-Pentane STO-3G
6-31G
1. Compute the energy difference between E(anti) and E(gauche) for n-Butane and n-
pentane using STO-3G and 6-31G basis set.
2. Compute the energy difference between E(anti) and E(eclipsed) for n-Butane and n-
pentane using STO-3G and 6-31G basis set.
3. Compute the energy difference between E(anti) and E(cis) for n-Butane and n-pentane
using STO-3G and 6-31G basis set.
4. Which basis set gives better result?
Result:
Energy of interconversion of n-butane from anti to eclipsed = ..... kcal/mol using 6-31G basis set
Energy of interconversion of n-butane from anti to gauche = ..... kcal/mol using 6-31G basis set
Energy of interconversion of n-butane from anti to cis = ..... kcal/mol using 6-31G basis set
Energy of interconversion of n-pentane from anti to eclipsed = ..... kcal/mol using 6-31G basis
set
Energy of interconversion of n-pentane from anti to gauche = ..... kcal/mol using 6-31G basis set
Energy of interconversion of n-pentane from anti to cis = ..... kcal/mol using 6-31G basis set